Condensation product of polycarboxylic halides with mineral oils and process for producing it



' to above the critical temperature of the Patented Sept. 21,

CONDENSATION PnopUc'r F roLrcAa- BOXYLIC nannies wrrn MINERAL oms, AND rnocnss Fon rnopoomd rr Eugene Lieber, West New Brighton, N. E, as-

signor to Standard Oil Development Company, a corporation of were No Drawing. Application July 1, 1941,

Serial No. 400,576

6 Claims. (01. 260-592) The present invention relates to improved lubricants and. more especially to waxy lubricating oils containing pour point depressants of a new type. The invention will be fully understood from the following description.

It has been found thatsuperior pour point depressants and thickeners can be produced by the condensation of the acid halides, obtained from polycarboxylic acids, with mineral oils. Heretofore acid halides have been condensed with aromatic compounds, but such materials as a;

rule are not useful as pour depressants. They also have certain other disadvantages which are well known to those skilled in the art. It has been discovered that the present depressants and thickeners made by the condensation of halides of-polycarboxylic acids with petroleum oils, especially with lubricating oils or extraction products They thereof, are particularly advantageous. may be made from all types of lubricating oils whether obtained from naphthenic, asphaltic or parafilnic groups, and are made from the residual as well as distillate oils and even from low boiling distillates such as gas oils and kerosene, boiling above the gasoline range.

,When making these materials from distillate oils, there is little. difiiculty encountered, but

when using residual oils, it is sometimes necessary to purify the oil before condensation in order to remove sludge, asphaltic and other very heavy molecular weight compounds. Thiscan be done by precipitation thereof with various asphalt precipitating agents. The best of this class of substances are the low specific gravity naphtha fractions and the liquefied, normally gaseous hydrocarbons such as ethane, propane, bu-

tane and various mixtures of these compounds. The precipitation may be accomplished under well known conditions either by reducing the temperature or by raising the temperature to the vicinity (above or below) of the critical point of the precipitant. Under the higher temperature process, it is necessary for the oils to be main tained under high pressure so as to maintain them in liquid condition. If the temperature is raised ipitant, asufiicient solution thereof in the o s or in a solvent added for the purpose is obtained to effect precipitation. vIn eithercase, the asphaltic and heavier compounds are precipitated and the purified oil may be separated either by decantation or filtration. 0

The acid halides used for the present purpose are preferably acid chlorides obtained from dicarboxylic acids which may be either aliphatic or aromatic. Among the diacyl halides that have been employed may be mentioned'the acid chlo-' rides of sebacic, succinic, adipic, oxalic and phthalic acids, but it will be understood that these are only examples to. illustrate the type of acid halide employed. Th

materials satisfactory for the present purpose, and that other halides, especially bromides may be employed, as well as halides of other acids.

, The reaction is carried out under the influence of catalysts, preferably those of the Friedel Crafts type such as aluminum chloride, zinc chloride, boron fluoride. titanium chloride or fluoride and their various known equivalents. It is generally desirable to employ a solvent such a's-a naphtha.

or an inert halogenated solvent such as tri or tetrachlor ethane, carbon disulfide or the like.

The diacyl halide and the petroleum oil frac-.

tions may vary considerably in proportions, but it has been found that'best results for producing pour depressing compounds are obtained where 100 parts by weight of the petroleum oil are used with from about 5 to 30 parts of the acid halide. Similarly the amount of catalyst may also vary, but it is usually desirable to employ at least one moi of aluminum chloride or other catalyst for each mol of the dicarboxylic amount of catalyst may be increased above th amount if desired, in order to increase the reaction and to make it proceed more smoothly.

The reaction time is dependent on the -proportion of ingredients and the amount of catalyst, as well as on the specific halide and oil employed, but in general reaction time is from it to 4 or 5 hours.

of an hour or two is usually sufiicient and at more elevated temperatures, for example up to about 200 F., the reaction is quite rapid. In many instances, the reaction is so vigorous that no heating whatever is required. Temperature and time of reaction are preferably adjusted so as to avoid the formation of solid, rubbery, insoluble, carbonaceous materials.

At the end of the reaction period, the mixture is preferably diluted with kerosene and then admixed with a relatively large volume of alcohol and water. Catalytic sludge is thus hydrolyzed and the kerosene layer, containing the desired products, may be decanted from the aqueous sludge layer. The depressant is recovered by distilling the kerosene and other diluent and is collected as the distillation residue.

The product produced as above is a viscous oily material of good appearance.

about /2 to 5% in order to producea'marked pour depression.

In producing products principally as thickening agents, it is most de- At room temperature, at which most ofv the halides react quite vigorously, a reaction time.

which are to be used Example I grams of sebacic acid were mixed with grams of phosphorous trichloride and heated on a water bath. When reaction was complete, the sebacyl chloride which has the formula was decanted off of the phosphorus acid solution and was mixed with 100 grams of Pennsylvania Bright Stock. This mixture was then dissolved in 200 cc. of tetrachlor ethane and 14 grams of anhydrous aluminum chloride were slowly added to the mixture which was maintained at room temperature while agitating. A vigorous reaction took place and hydrochloric acid gas was rapidly evolved. The catalyst was added over a period of about one hour and after the addition thereof,

the reaction was warmed on the water bath to about 80 C. for an additional period of 30 minutes.

At the end of this period the mixture was diluted with 1,000 cc. of kerosene and poured into a large volume of the alcoholand-water. The kerosene layer was decanted from the aqueous layer and was distilled with fire and steam to 600 F. in order to remove the solvent, kerosene and the lower boiling fractions of the condensation product. In this manner, a residue amounting to 96 grams was obtained.

The original Pennsylvania oil had a viscosity of 143 sec. Saybolt at 210 and the recovered condensation product had a viscosity of 533 sec. at 210.

When 5% of the condensation product was added to a waxy mineral oil, the original pour point of +30 F. was reduced to F.

Erample II Another pour depressant was made using the same procedure as in Example I, except that the reagents were changed as follows:

Pennsylvania Bright Stock "grams..- 150 Tetrachlorethane cc 300 Sebacic acid rams Phosphorous trichloride do AlCla do 81 15 grams of adipic acid were mixed with 15 grams of phosphorous trichloride on the water bath. The adipyl chloride was then collected just as described in Example I and to the total amount of adipyl chloride collected were added grams of Pennsylvania Bright Stock and 300 grams of tetrachlor ethane for use as a solvent. This mixture was put into a. three liter flask which was provided with a stirring rod and an outlet for gaseous reaction products. 60 grams of AlCls were then added slowly so the temperature was maintained at 80 F. for a period of one hour. It was then cooled to room temperature and maintained for an hour longer. It was then heated to between F. and F. for two hours and diluted with 1,000 cc. of kerosene. This mixture was then poured into a large volume of alcohol and water as in Example I and 100 grams of a viscous oil were obtained on distilling the kerosene layer. The product had a viscosity of 4169 sec. Saybolt at 210 F., and an addition of 5% thereof to an oil having an original pour point of 30 F., it was found that the pour point was reduced to 10 F.

Example IV Experiment 3 was repeated except that 30 grams of AlCh were used and 100 grams of a viscous oily product having a viscosity. of 888 sec. at 210 were collected. This material when 5% was added to an oil having a pour point of +30 F., produced a reduction to 0 F.

Example V The following example illustrates the preparation of a pour depressor substance from a gas oil.

Sebacyl chloride was prepared by treating 20 grams of sebacic acid with 20 grams of phosphorous trichloride on the water bath. When the reaction was complete, the sebacyl chloride was decanted from the phosphorous acid into a mixture of'200 grams of a Columbian gas oil dissolved in cc. of tetrachlorethane as solvent. 28 grams of AlCh was slowly added to this mixture at room temperature and no attempt was made to cool the reaction mixture. Very vigorous reaction took place as evidenced by the evolution of hydrogen chloride gas. Thirty minutes were required to add the AlCls. After the addition of the AlCla, the reaction mixture was heated to 90 C. and maintained thereat with stirring for 60 minutes. The reaction mixture was then neutralized as described in Example I. The kerosene extract was distilled with fire and steam to 600 F. to remove low boiling materials. 69 grams of a heavy green oil was obtained.

The original Columbian gas oil had a viscosity of 50 sec. Saybolt at 100 F. and the recovered condensation product had a viscosity of 210 sec. Saybolt at 210 F. When 1% of the condensation product was added to a. waxy mineral oil, the original pour point of +30 F. was reduced to 0 F. When 5% of the condensation product was added to the same waxy mineral oil, the pour point was reduced to 10 F.

Example VI Another pour depressor was made using the same procedure as in Example V, except that the reagents were changed as follows:

After recovery and removal of low boiling products, 103 grams of a viscous residue was obtained. when 5% of this condensation product was added to a waxy lubricating oil having a pour point of +30 F., it was found to be reduced to F.

Example VII The following example will illustrate the preparation of a pour depressor from a total distillate Grams Spindle oil 200 Sebacic .aoid- 20 A101: 28

After recovery and removal of low boiling products, 83 grams of a deep green viscous oil was obtained.

The original spindle oil had a viscosity of 52.8 sec. Saybolt at 210 F. and the recovered condensation product had a viscosity of 253 sec. Saybolt at 210 F.

The pour depressor properties of the condensa tion product was tested by blending in a waxbearing oil. The following data was obtained:

Pour point, F.

.Waxy-oil +30 Waxy-oil +1% condensation product.--" +20 Waxy-oil +2% condensation product 5 Waxy-oil +5% condensation'product Example VIII The following example will illustrate the preparation of pour depressors from kerosene.

The experimental procedure of Example V was 0 followed exactly except that the following reagents were used:

Grams Kerosene (aniline point, 35 F.) 200 'Sebacic acid 20 Al Cl3 2s After recovery and removal of low boiling products, 48 grams of a green viscous'oil was obtained.

, When 5% of the condensation product was added to a waxy mineral oil, the original pour point of +30 F. was reduced to 0 F.

Ewample 1x The oil thickening and V. I. improving properties of the products of my invention is illustrated by the following example.

The condensation product of Example II having a viscosity of 4190 sec. Saybolt at 210 F. was

blended into a spindle oil and the change in V. I.

As a comparison, the original Penn noted. Bright Stock was also tested. The following re-.- sults were obtained.

The present products can be used as wax modifiers for various purposes,v for example, to

assist in separation of wax from oils by filtration, settling and centrifugation of diluted oil which is chilled to the wax precipitation point. Small amounts of the modifier greatly increase 5 ease of separation. A

The condensation products of this invention may be used as plasticizers in various products such as in rubber, resins, etc. In certain cases where the condensation products themselves are hard solids, they may be used as resins. They may be compounded in waxes, paraffin wax, vegetable waxes, etc. They impart special properties due to their high molecular weight and the presence of petroleum hydrocarbon groups chemically combined therein. They may be used as chemical intermediates for making other chemicals, such as nitriles, etc. They can be sulfated, and used in the form of soaps, dispersion agents, etc. This application is a continuation-in-part of application Serial No. 230,813 filed September 20,

The present invention is not to be limited by any theory of the mechanism of the reaction nor to any particular reagents or catalysts, 'but i only to the following claims in which it is desired to claim all novelty inherent inthe invention.

I claim:

1. The process which comprises chemically condensing a polycarboxylic acid halide with a mineral oil, using a Friedel-Crafts catalyst, and distilling the reaction product with fire and steam up to about 600 F. to recover the desired condensation product as a viscous distillation residue.

2. The process which comprises subjecting to a Friedel-Crafts condensation, a dicarboxylic acid halide and a petroleum oil fraction boiling above gasoline, at a .temperature between about room temperature and about 200 F., for a reaction 40 Period of about /2 to 5 hours, removing the catalyst, and distilling the reaction product with fire and steam up to about 600 F. to recover the desired condensation product as a viscous distillation residue.

3. The process which comprises subjecting to a Friedel-Crafts condensation about 5 to 30 parts of dicarboxylic acid chloride having the general formula ClOC(CH2)nCOCl,where n is zero to 8, and 100 parts of a petroleum oil boilin above the gasoline range, at a temperature between.abo.ut room temperature and about 200 F., for a period of about /z to 5 hours, using at least about 1 mol of aluminum chloride to 1v mol of the acid halide, stopping the reaction b fo formation of insoluble solid rubbery products,

diluting the reaction product with kerosene, hy-

drolyzing and removing residual. catalyst, and distilling the reaction product mixtureby fire and steam to about 600 F. to obtain the desired residue.

4. Viscous oily product madeby the process of claim 1. v 5. Product of the process of claim 2, said product being a viscous, oily product soluble in mineral oil.

.6. Product of-the process of claim 3, said product being a viscous, oily product soluble in mineral oils and having the property of depressing the pour point of wax mineral oil when added thereto in small amounts.

-' EUGENE LIEZBER. 

